Method of combating nematodes, and nematocidal preparations



United States Patent 3,178,338 METHOD OF COMBATING NEMATODES, AND NEMATOCIDAL PREPARATIONS Adolf Em g ifit, Basel, and. Rudolf Anliker, Biuningen,

Switzerland, assig ors to Ciba Limited, Ba el, Switzerland, a company of Switzerland No Drawing. Filed Dec. 18, '1962, Ser. No. 245,433 Claims priority, application Switzerland, Dec. 28, 1961, 15,113/ 61 Claims. (Cl. 167-63) The present invention provides nematooidal preparations containing as active principle 1:13 :4-thiadiazo1e-thiophene compounds of the general formula (1) RFOC R3 S in which R represents a hydrogen or chlorine atom, or an alkyl group with l to. 4 carbon atoms, or the group in which X is an oxygen or sulfur atom; R and R may be identical or different and each represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and R represents a mononuclear or binuclear aromatic radical which may be substituted by one or several lower .alkyl or alkoxy groups or halogen atoms, or a S-menrbered or 3,178,338 Patented Apr. 13, 1965 "ice following additives: Solvents with a boiling point of at least C., solid carriers, dispersants, wetting or adhesive agents, fertilizers, and other pesticides.

Particularly valuable. preparations. for combating nematodes-more especially nematodes that cause damage in agriculture or horticulture-are those which contain as the active principle a compound of the general Formula 1 in which R represents a hydrogen atom or a methyl group or the group in which X represents an oxygen or sulfur atom; R; stands As examples of compounds of the general Formula 1 to be used according to invention there may be men- 6-membered heterocyclic radical and at least one of the 30 rtioned the compounds listed in the following Table 1:

Table 1 Anal sis molecular wei ht Formula P pe ties y a Qalculated Eound 1 H.COH S, HC, CH Light yellow, fine, shiny C, 47:97- C, 47.92.

1 n n' n needles, M.P., 1512-15187 0. H, 2.42 H, 2.724. H0 C-C C-C CH .(ethan'ol). N', 11.19 N, 11.30.

\ II I! -3 S N- S (250.37)

2 H CH S Colorless, very fine needles 0 51.70 C, 51161.

H 11 M.P.,168.6-:=169.2 c. H, 2.53 H, 2.34. HC\ /C+-(J ("3 I Cl (dioxane+wa ter 2:1). N, 10.05; N, 10.03.

278.79 S N -N 3 HCCH S HC CH S HC-CH Yellow shiny, fine flakes, C 46. C, 45.85.

H n u u u n memii above 300 0. (ortho- H, .94 H, 1.93. HO\ /C-%I) fi0\ /C[) ("3C\ /GH dichlorobenzene). N, 13. N, 13.67.

S, 38.49 S, 3829. S NN S NN S ($16.60)

4 HCCH S Pale-yellow, flakes, M.P., C, 60. C, 60.57.

H I] 137.2-138" c. (e haploid-Water 11,3.90 H, 3.93. HC\ /C(3 fi- CH3 2:1). N, 10. N, 10.91.

2 S N N 58 6) 5 HC H S OH; Colorless, felted needles,M.P., 0, 62,96 0, 63,71.

n 109.4 C. '(etha Ql-l-water 5,37- H, 54s HO\ /CH H H- (ll-CH 4:1). N, 955%.; N, 9.20.

CH 6 HC S I Colorless, shiny flakes, M.P., C, 61.96.

1701-1112" 0. (ethanol+ H, 4.40. H 0 C0 C CH; water 3:1). N, 10.14.

\ II 11 N N Cl 7 HCCH S Colorless, shiny needles, M.P., 0, 51,70 C, 51.82.

11 u 122.2-122.s 0. (ethanol). H, 2.53 H, 2.39. HC\ o- 1 N, 13,05 N, 9.80.

Cl 8 S I Colorless, very fine needles, 0, 46.01 C, 46.41.

ll H M.P., 179.5?180 0. (ethanol 11, 1.93 H, 1.88. HO C-C C -Cl +Water 9:1). N, 8.94 N, 8.98.

Table 1-Continued m m m e 3 .6 5 1 w o 0 53 m F mm H? mm QHN QHN RN 8 0 H m m m m m m m M m m n u n u h "D 5 w m ain 953% M 9 A ofiN QHN GEN oEN P. mw 0. m u C 1 2 6 P r M mm 2: d m r u. 4 r e 1 6 E r y .t mm m mmm mm M 7 Mwm m Hm mm mm mu mmm k Y( s 16 6L, 1 t H PM e mi mum a? @HH m? e, H mw m5 um PM m $0 Mm Km vmm mwm mm mm mum mwq Mm e 1 y 7 1 v y a w 1 0 m m m mm Hm m m Hm Hm mum Hm m w P w M m? sM+ MM+ WM+ M+ 27 w m hw mum/w ow omr mea 1e 1,1 1e 0d w 1 H x 0 Ha n1 qm 0 3 m $3 w M00 2% cub H m bno wk. m m was). m h m w h 5m 5w EB 6 m mM m fi m m M e E m 111. O v I\ e 2 m A A m A 0 m A Q M F.111 I6 H z c a m a H H H H 1 1 C H c c c c 0 0 0 o C H 3 w 3 o C H 1 H 3 CI: C 3 C m H H m a 3 0 0 m H H N 0 F 0 0 g 0 0| c N G N o N c N c N C N 0 N N N N V O O 0" C N C N G N S s S S S S S S 3 CNN 3 CNN a CHIN 3 CNN 2 CNN 2 CNN a CNN H H H H H H H CNN cHN CNN oHN oHN C"N c c o c o e c o e c o e c o e c o e c one i i i m H w H w a /s /s /s /s /s /S l l I 1 l S S S S S S 0 0 C10 C10 CIC CIC CHC CH0 H H H H H H H C 0 C 0 C 0 C 0 C 0 C 0 m. a. m. a w m w H H H H H H H H H H H H H H H H H H H n n n u n u n u u n n n m m u u n n u n u n n u n N n u n u n u n u u n u n n u n u n n n n n u u n 9 1 n H H M H m -1 m w mu Table 1-Continued Analysis (molecular weight) No. Formula Properties 7 V V 7 Calculated Found OHa l CH3 22 C S l Pale-yellow, very fine, felted H H needles, M.P., 1s2-1s2.5 o. H C-0 /C.- H t]? -0 CH; (dioxane+water 1:1).

(BBQ 23 HC C S HC -CH Pale-yellow, fine crystalline II II ll 1] powder, M.P., 142.8-144.2 HzC-O C-- 0-0 CH C. (methanol-l-water 2:1).

n n S N 0 0 CH 24 HC-- S Pale-yellow, very fine needles,

H H M.P., 158.8-159.1 0. (ethanol HC\ /C(|% El] 0 CH5 +water 3:4).

S N N 25 CH S Colorless, very fine needles,

II [I M.1 134.94354 0. (ethanol HO C0 0 +water 1:1).

i 26 HC. S Light-yellow, shiny needles,

H H 163.2165.2 o. H3CO (3-0 G (ethanol+water 2: 1).

ll I! S V N (IJHa 2 7 CC S Pale-yellow, very fine, felted H II needles, M.P., 133.2135 0. H3CC C-C C (ethanol+water 1:2).

II II N 2 S -N 28 HC-C S HCCH 8 HC OH Yellow, fine, crystalline powder C, 49.98 C, 49.98.

H H 11 ll II [I melting above 300 0. (orthon, 2.10 H, 2.25. HG 0-0 C-0 C0 0- CH dichlorobenzene). N, 1 .57 N, 14.68.

\ I! II i! 11 (384.47)

The manufacture of the active principles of the general Formula 1 incorporated with the agents of the invention has been described in detail in British Patent No. 900.815, granted October 31, 1962 to Ciba Limited.

The active principles of the general Formula 1 may be used as solutions, emulsions or dispersions or as dusting agents, by themselves or in admixture with the aforementioned additives, for example in conjunction with fertilizers, ammonium salts, phosphates, calcium cyanarnide or urea, and also with pesticides, for example chlorinated hydrocarbons, carbamates, thiocarbamates, phosphoric acid esters and the like.

The new agents may further contain identifying agents, bactericides, fungicides and additional nematocides.

Aqueous sprays containing active principles of the general Formula 1 may be prepared from emulsion concentrates, pastes or wettable spray powders by the addition of water, for example by grinding with sulfite cellulose waste liquor. Further suitable emulsifiers or dispersants are non-ionic products, for example condensation products of aliphatic alcohols, amines or carboxylic acids containing a long-chain hydrocarbon radical con taining about to 30 carbon atoms with ethylene oxide, such as the condensation product from octadecyl alcohol with to mols of ethylene oxide, or from soybean fatty acid with 15 mols of ethylene oxide, or from soybean fatty acid with 30 mols of ethylene oxide, or from commercial olcylamine with 15 mols of ethylene oxide, or from dodecylmercaptan with 12 mols of ethylene oxide.

From among suitable anionic emulsifiers there may be mentioned: the sodium salt of dodecyl alcohol sulfuric acid ester, the sodium salt of dodecylbenzenesulfonic acid, the potassium or triethanolamine salt of oleic or abietic acid, or of mixtures of these acids, or the sodium salt of petroleum-sulfonic acid.

Suitable cationic dispersants are, for example, quaternary ammonium compounds, such ascetyl pyridinium bromide or dihydroxyethyldodecyl ammonium chloride.

For the manufacture of solutions for direct spraying there may be further added organic solvents boiling above 10Q C. for example, mineral oil fractions, such as Diesel oil or kerosene, also coal tar oils and oils of vegetable or animal origin, as well as hydrocarbons such as alkylated naphthalenes or tetrahydronaphthalene, if desired with concomitant use of mixtures of xylene, cyclohexanols or kctones; also chlorinated hydrocarbons such as tetrachloroethane, trichloroethylene or trichlorobenzenes or tctrachlorobcnzenes.

For the manufacture of dusting or strewing materials there may be used as solid vehicles talcum, kaolin, bentonite, calcium carbonate, calcium phosphate or coal, cork meal or wood meal or other materials, of vegetable origin. It is very advantageous to prepare the materials in the form of granulates. The new products in their various forms of application may be admixed in known manner with substances that improve the distribution, adhesion, stability towards rain or the penetration power. As such substances there may be mentioned fatty acids, resins, glue, casein and alginatcs.

The following examples illustrate the invention. The parts are parts by weight.

EXAMPLE 1 The compound shown under (1) in the above Table 1 was mixed with aqueous sulfite cellulose waste liquor and very finely ground. A series of dilution from 200 parts 3,178,338 7 8 per million downwards with the dilution factor 2 was consisting of the hydrogen atom, the chlorine atom, alkyl prepared by mixing the microdisperse preparation thus containing 1 to 4 carbon atoms, and obtained with water. 10 ml. each of the liquor were dropped through a pipette into a Petri dish and 10 ml.

of a suspension of the nematodes Anguina tritici, Ditylen- 5 i F chus dipsaci and Heteroa'era schachtz'i respectively were H added. The Petri dishes were covered and kept for 6 days in difiuse daylight. The broth was then filtered off,

the filter residue rinsed with 1 liter of water and then placed for 24 hours on a cotton wool filter infested with in which X represents a member Selected from the group nematodes. The surviving nematodes were able to work consisting of the oxygen atom and the sulfur atom, R their way through the filter and to collect in a pipette and R each represents a member selected from the group and were then counted. The nematocidal effect achieved consisting of the hydrogen atom and alkyl containing is shown in the following Table 2: 1 to 4 carbon atoms, and R represents a member selected Table 2 ACTIVE PRINCIPLE: 2:5-[DITHIENYL-(2)]-1:3z4-THIADIAZOLE from the group consisting of phenyl, a phenyl substituted Ditylenchus dipsaci. by at most 2 chlorine atoms, a phenyl substituted by at most 2 alkyl containing at most 4 carbon atoms, a phenyl EXAMPLE 2 substituted by methoxy, a phenyl substituted by methoxy The test for nematocidal effects described in Example and alkyl containing at most 4 carbon atoms, thienyl, di-

1 was performed, using as active principle the compound phenyl, naphthyl, pyridyl and furyl. (2) in Table 1. The nematocidal efiect thus achieved 2. A method as claimed in claim 1, wherein the objects is shown in the following Table 3: which are to be protected from the nematodes are treated Table 3 ACTIVE PRINCIPLE: 2-[THIENYL-(2)]-5-[4'-CHLOROPHENYL-(1')-1:3:4-

THLADIAZOLE Good nematocidal effects were also achieved against Good nematocidal efiects were also achieved against with a nematocidal amount of the compound of the Ditylenchus dipsaci. formula EXAMPLE 3 ncon s H a The test for nematocidal eifects described in Example HQ) ii-o G-ii I H 1 was performed, using as active principle the compound it (3) in Table 1.

The nematocidal effect thus achieved is shown in the following Table 4:

3. A method as claimed in claim 1, wherein the objects which are to be protected from the nematodes are treated Table 4 with a nematocidal amount of the compound of the formula HC CH S at LG C@ a S l l Rr- G CR4 II II S 4. A method as claimed in claim 1, wherein the 0bin which R represents a member selected from the group 75 jects which are to be protected from the nematodes are What is claimed is:

1. A method for combating nematodes which are harmful in agriculture and horticulture, wherein the objects which are to be protected from the nematodes are treated Wtih a nematocidal amount of a compound of the formula treated with a nematocidal amount of the compound of in which R represents a member selected from the group consisting of the hydrogen atom, the chlorine atom, alkyl containing 1 to 4 carbon atoms, and

in which X represents a member selected from the group consisting of the oxygen atom and the sulfur atom, R and R each represents a member selected from the group consisting of the hydrogen atom and alkyl containing 1 to 4 carbon atoms, and R represents a member selected from the group consisting of phenyl, a phenyl substituted by at most 2 chlorine atoms, a phenyl substituted by at most 2 alkyl containing at most 4 carbon atoms, a phenyl substituted by methoxy, a phenyl substituted by methoXy and alkyl containing at most 4 carbon atoms, thienyl, diphenyl, naphthyl, pyridyl and furyl, and in addition thereto a member selected from the group consisting of an organic solvent boiling above 100 C., water, a dispersing agent, a wetting agent and a solid carrier.

References Cited by the Examiner FOREIGN PATENTS 900,815 10/62 Great Britain.

JULIAN S. LEVI'IT, Primary Examiner. 

1. A METHOD FOR COMBATING NEMATODES WHICH ARE HARMFUL IN AGRICULTURE AND HORTICULTURE, WHEREIN THE OBJECTS WHICH ARE TO BE PROTECTED FROM THE NEMATODES ARE TREATED WITH A NEMATOCIDAL AMOUNT OF A COMPOUND OF THE FORMULA 